EP3671191B1 - Kalibrierverfahren ausgeführt durch eine analysevorrichtung - Google Patents

Kalibrierverfahren ausgeführt durch eine analysevorrichtung Download PDF

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Publication number
EP3671191B1
EP3671191B1 EP19216693.2A EP19216693A EP3671191B1 EP 3671191 B1 EP3671191 B1 EP 3671191B1 EP 19216693 A EP19216693 A EP 19216693A EP 3671191 B1 EP3671191 B1 EP 3671191B1
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Prior art keywords
specimen
energy
spectrum
detection regions
diffraction grating
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French (fr)
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EP3671191A3 (de
EP3671191A2 (de
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Takanori Murano
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Jeol Ltd
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Jeol Ltd
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/207—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions
    • G01N23/2076—Diffractometry using detectors, e.g. using a probe in a central position and one or more displaceable detectors in circumferential positions for spectrometry, i.e. using an analysing crystal, e.g. for measuring X-ray fluorescence spectrum of a sample with wavelength-dispersion, i.e. WDXFS
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/2209—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using wavelength dispersive spectroscopy [WDS]
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/07—Investigating materials by wave or particle radiation secondary emission
    • G01N2223/079—Investigating materials by wave or particle radiation secondary emission incident electron beam and measuring excited X-rays
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N2223/00—Investigating materials by wave or particle radiation
    • G01N2223/30—Accessories, mechanical or electrical features
    • G01N2223/303—Accessories, mechanical or electrical features calibrating, standardising
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/225—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion
    • G01N23/2251—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material using electron or ion using incident electron beams, e.g. scanning electron microscopy [SEM]
    • G01N23/2252—Measuring emitted X-rays, e.g. electron probe microanalysis [EPMA]

Definitions

  • the present invention relates to a calibration method executed by an analysis device.
  • a specimen is irradiated with a primary beam such as an electron beam or an X-ray, and X-rays emitted from the specimen are detected.
  • a primary beam such as an electron beam or an X-ray
  • Energy-dispersive X-ray spectrometry in which composition information about a specimen is acquired by irradiating the specimen with an electron beam in an electron microscope and detecting X-rays emitted from the specimen, is an example thereof.
  • Energy-dispersive X-ray spectrometry uses the fact that characteristic X-rays have energy values that are unique to the elements constituting the specimen. On a spectrum of characteristic X-rays acquired by energy-dispersive X-ray spectrometry, element types contained in the specimen are determined from the energy values of the peaks, and the content of each element type is determined from the surface area of the corresponding peak.
  • a method using a soft X-ray emission spectrometer in which a diffraction grating is combined with a charge-coupled device (CCD) camera, is known as another example of the method described above.
  • SXES soft X-ray emission spectrometer
  • CCD charge-coupled device
  • the energy axis of the spectrum is calibrated by measuring a standard specimen in order to acquire a soft X-ray spectrum, and correcting the energy axis from the positions of the peaks (the energy values of the peaks) on the acquired spectrum and logically or empirically determined energy values using a polynomial approximation.
  • the energy range between the peaks used in the correction can be corrected comparatively precisely. Outside the energy range between the peaks used in the correction, however, the precision deteriorates dramatically.
  • JP 2001 356050 A discloses a spectroscopic method with small errors, a method for measuring a thickness and a method using these methods for forming films.
  • An incident light is brought into a light dispersion means to split the light for each wavelength.
  • the split light of each wavelength is brought into a conversion means for converting the light to an electrical signal corresponding to an intensity of the light.
  • the wavelength of the light entering a specific position on the conversion means is determined by a calibration expression derived from characteristics of the light dispersion means.
  • a calibration method executed by an analysis device the analysis device including:
  • energy of the signal detected in each of the plurality of detection regions can be determined from a logical expression of the spectroscopic element based on the positional relationship between the specimen and the spectroscopic element and the positional relationship between the spectroscopic element and each of the plurality of detection regions. According to this calibration method, therefore, in contrast to a case in which calibration is performed using a polynomial approximation, for example, energy of the signal detected in each of the plurality of detection regions can be determined precisely over the entire range of energy values that can be detected by the detector.
  • the analysis device includes
  • energy of the signal detected in each of the plurality of detection regions is determined from a logical expression of the spectroscopic element based on the positional relationship between the specimen and the spectroscopic element and the positional relationship between the spectroscopic element and each of the plurality of detection regions. According to this analysis device, therefore, in contrast to a case in which calibration is performed using a polynomial approximation, for example, energy of the signal detected in each of the plurality of detection regions is determined precisely over the entire range of energy values that can be detected by the detector.
  • FIG. 1 illustrates a configuration of an analysis device 100.
  • the analysis device 100 includes an electron beam emitting unit 10, an X-ray focusing mirror 20, a diffraction grating 30, an X-ray detection device 40, a display unit 50, an operating unit 52, a storage unit 54, and a processing unit 60.
  • the electron beam emitting unit 10 irradiates a specimen S with an electron beam.
  • the electron beam emitting unit 10 includes an electron gun serving as an electron beam source, and an illumination-lens system for irradiating the specimen S with the electron beam emitted from the electron gun.
  • the analysis device 100 may also function as a scanning electron microscope for acquiring a scanning electron microscope image (a SEM image).
  • an electrostatic deflection plate 12 or a magnetic deflector, for example, is disposed above the specimen S.
  • characteristic soft X-rays also referred to simply as "X-rays” hereafter
  • backscattered electrons, secondary electrons, and so on are also generated from the specimen S.
  • the electrostatic deflection plate 12 By disposing the electrostatic deflection plate 12, the backscattered electrons, secondary electrons, and so on can be removed.
  • the potential applied to the electrostatic deflection plate 12 is variable, and by applying the potential in accordance with the accelerating voltage of the electron beam, background can be reduced.
  • the X-ray focusing mirror 20 focuses the X-rays emitted from the specimen S and guides the focused X-rays to the diffraction grating 30.
  • the intensity of the X-rays entering the diffraction grating 30 can be increased.
  • the measurement time can be reduced, and the S/N ratio of the spectrum can be improved.
  • the X-ray focusing mirror 20 is constituted by two mutually opposing mirrors, for example.
  • the interval between the two mirrors is narrow on the specimen S side (the entrance side) and wide on the diffraction grating 30 side (the exit side).
  • the quantity of X-rays entering the diffraction grating 30 can be increased.
  • the diffraction grating 30 diffracts the X-rays that are generated from the specimen S when the specimen S is irradiated with the electron beam.
  • X-rays diffracted into respective wavelengths (energy values) can be acquired.
  • the diffraction grating 30 is an unequal interval diffraction grating, for example, in which grooves are formed at unequal intervals for the purpose of aberration correction.
  • the diffraction grating 30 is configured such that when X-rays enter at a large incident angle, the focus of the diffracted X-rays is formed on a detection plane 43 of an image sensor 42 rather than on the Rowland circle.
  • the X-ray detection device 40 is configured to include the image sensor 42 (an example of a detector) and a control device 44.
  • the image sensor 42 detects the X-rays (diffracted X-rays) diffracted by the diffraction grating 30.
  • the image sensor 42 is highly sensitive to soft X-rays.
  • the image sensor 42 is a charge-coupled device (CCD) image sensor, a complementary MOS (CMOS) image sensor, or the like, for example.
  • CMOS complementary MOS
  • the image sensor 42 is a back-illuminated CCD image sensor, for example.
  • the image sensor 42 is positioned so that the detection plane 43 is aligned with an image plane of the diffracted X-rays.
  • FIG. 2 is a schematic plan view illustrating the detection plane 43 of the image sensor 42.
  • the image sensor 42 includes a plurality of detection regions 2 arranged in an energy dispersion direction A. Hence, in the image sensor 42, X-rays diffracted by the diffraction grating 30 so as to have different energy values (wavelengths) are detected independently.
  • Each detection region 2 corresponds to one pixel of the image sensor 42, for example. Note that the detection region 2 may also be constituted by a plurality of adjacent pixels of the image sensor 42.
  • the plurality of detection regions 2 are also arranged in an X-ray spreading direction B of the image sensor 42.
  • the spreading direction B is orthogonal to the energy dispersion direction A.
  • X-rays having identical energy values (wavelengths) can be detected.
  • the control device 44 controls the image sensor 42 in FIG. 1 .
  • the control device 44 supplies power to the image sensor 42. Further, the control device 44 executes processing for transmitting an output signal from the image sensor 42 to the processing unit 60.
  • the control device 44 includes a cooling mechanism for cooling the image sensor 42 and thereby controls the temperature of the image sensor 42.
  • the display unit 50 outputs an image generated by the processing unit 60.
  • the display unit 50 can be realized by a display such as a liquid crystal display (LCD), for example.
  • LCD liquid crystal display
  • the operating unit 52 executes processing for converting instructions from a user into signals and transmitting the signals to the processing unit 60.
  • the operating unit 52 can be realized by an input device such as buttons, keys, a touch panel display, or a microphone, for example.
  • the storage unit 54 stores programs and data used by the processing unit 60 in various calculation processing and various control processing.
  • the storage unit 54 is also used as a work area of the processing unit 60.
  • the storage unit 54 can be realized by a random access memory (RAM), a read only memory (ROM), a hard disk, and so on, for example.
  • the processing unit 60 executes processing for generating an X-ray spectrum based on the output signal from the image sensor 42. Further, the processing unit 60 executes control for displaying the generated spectrum on the display unit 50.
  • the functions of the processing unit 60 can be realized by executing a program using various processors (a central processing unit (CPU) or the like).
  • the processing unit 60 includes a spectrum generation unit 62 and a display control unit 64.
  • the spectrum generation unit 62 executes processing for determining the energy (wavelength) of the X-ray detected in each of the plurality of detection regions 2 based on a positional relationship between the specimen S and the diffraction grating 30 and a positional relationship between the diffraction grating 30 and each of the plurality of detection regions 2.
  • the spectrum generation unit 62 then executes processing for acquiring information indicating the intensity of the X-ray detected in each the plurality of detection regions 2 from the output signal output by the image sensor 42 and generating a spectrum based on the intensities.
  • the display control unit 64 executes control for displaying the spectrum generated by the spectrum generation unit 62 on the display unit 50. Note that the processing executed by the spectrum generation unit 62 and the display control unit 64 will be described in detail below.
  • calibration of the energy axis includes a case in which an axis representing the positions of the detection regions 2 is converted into an energy axis and a case in which a set energy axis is corrected in order to set a new energy axis.
  • the case in which an axis representing the positions of the detection regions 2 is converted into an energy axis will be described below.
  • the calibration method according to the invention includes a step of determining the energy of the X-ray detected in each of the plurality of detection regions 2 based on the positional relationship between the specimen S and the diffraction grating 30 and the positional relationship between the diffraction grating 30 and each of the plurality of detection regions 2.
  • FIG. 3 is a flowchart illustrating an example of the calibration method according to this embodiment of the invention.
  • a standard specimen is measured and a spectrum is acquired.
  • the analysis device 100 when the specimen S is irradiated with an electron beam by the electron beam emitting unit 10, X-rays are generated from the specimen S.
  • the X-rays generated from the specimen S are focused by the X-ray focusing mirror 20 and then enter the diffraction grating 30.
  • the X-rays entering the diffraction grating 30 exit at exit angles corresponding to the wavelengths (energy values) thereof and then enter the detection plane 43 of the image sensor 42.
  • the X-rays entering the detection plane 43 are detected by the plurality of detection regions 2 arranged in the energy dispersion direction A. Information indicating the intensity of the X-ray detected in each of the plurality of detection regions 2 can be acquired from the output signal output by the image sensor 42.
  • FIG. 4 schematically illustrates a spectrum acquired by measuring the standard specimen.
  • the energy axis has not been calibrated, and therefore the horizontal axis of the spectrum in FIG. 4 indicates the positions of the detection regions 2 in the energy dispersion direction A.
  • the horizontal axis of the spectrum in FIG. 4 represents the positions of the detection regions 2 such that a single detection region 2 corresponds to a single pixel.
  • the vertical axis of the spectrum in FIG. 4 represents the intensities of the X-rays detected in the detection regions 2.
  • the energy values of the peaks of the spectrum in FIG. 4 are measured using a standard specimen and are therefore known.
  • the standard specimen is a specimen in which the energy values of the peaks appearing on the spectrum acquired when the specimen is measured by the analysis device 100 are known.
  • peaks appear respectively in a P1 pixel, a P2 pixel and a P3 pixel.
  • the spectrum in FIG. 4 is measured using a standard specimen, and therefore the energy values of the three peaks are known.
  • the energy value of the peak of the P1 pixel is E1eV
  • the energy value of the peak of the P2 pixel is E2eV
  • the energy value of the peak of the P3 pixel is E3eV.
  • FIG. 5 illustrates the positional relationship between the specimen S and the diffraction grating 30 and the positional relationships between the diffraction grating 30 and the image sensor 42. Note that for convenience, FIG. 5 only illustrates the specimen S, the diffraction grating 30, and the image sensor 42 among the constituent members of the analysis device 100.
  • d is the grating constant (the grating period) of the diffraction grating 30.
  • m is the diffraction order. Note that the diffraction order m is basically 1.
  • ⁇ is the wavelength of the X-ray.
  • ⁇ is the incident angle at which the X-ray enters the diffraction grating 30.
  • ⁇ is the exit angle of the X-ray diffracted by the diffraction grating 30.
  • a horizontal distance from the diffraction grating 30 to the detection plane 43 is set as D.
  • the height of the imaging position of the X-ray on the detection plane 43 or in other words the height of a detection region 2a (see FIG. 2 ), which is the detection region 2 in the position where an image of the X-ray is formed, is set as H.
  • the height H is the height of the detection region 2a relative to a diffraction plane 31 of the diffraction grating 30.
  • the direction of the height H matches the energy dispersion direction A in FIG. 2 .
  • the pitch (the pixel pitch) of the detection regions 2 in the energy dispersion direction A is 13.5 ⁇ m, for example, and when the position of the detection region 2a in the energy dispersion direction A corresponds to a P pixel, the height H of the detection region 2a is expressed by the following expression (1).
  • H h + P ⁇ 13.5 ⁇ 10 ⁇ 3 mm
  • h is the height of the detection plane 43 (the image sensor 42) relative to the diffraction plane 31 of the diffraction grating 30.
  • the exit angle ⁇ is acquired from the horizontal distance D from the diffraction grating 30 to the detection plane 43 and the height H of the detection region 2a in which an image of the X-ray is formed, and is expressed by the following expression.
  • tan ⁇ H / D
  • the wavelength ⁇ of the X-ray has the relationship of the following expression and can therefore be converted into the energy E of the X-ray. ⁇ ⁇ 1240 / E
  • optimal solutions of the parameters are determined by the method of least squares or the like using data sets of peak positions and energy values, acquired from the spectrum in FIG. 4 .
  • a set of the P1 pixel and E1eV, a set of the P2 pixel and E2eV, and a set of the P3 pixel and E3eV are acquired.
  • the incident angle oc, the distance D, and the height h are parameters relating to the optical arrangement of the diffraction grating 30 and the image sensor 42.
  • these parameters relate to the positional relationship (the optical positional relationship) between the specimen S and the diffraction grating 30 and the positional relationship (the optical positional relationship) between the diffraction grating 30 and the image sensor 42.
  • the incident angle ⁇ can be adjusted by modifying the position (the height) Hs of the specimen S.
  • the incident angle ⁇ is a parameter determined according to the positional relationship between the specimen S and the diffraction grating 30.
  • the distance D can be adjusted by modifying the position of the diffraction grating 30 or the position of the image sensor 42.
  • the height h can be adjusted by modifying the position of the image sensor 42 (the position of the detection plane 43).
  • the distance D and the height h are parameters determined according to the positional relationship between the diffraction grating 30 and the image sensor 42.
  • the energy (the wavelength) of the X-ray detected in each of the plurality of detection regions 2 arranged in the energy dispersion direction A are determined univocally by acquiring the optimal solutions of the incident angle oc, the distance D, and the height H.
  • FIG. 6 is a graph on which the horizontal axis of the spectrum in FIG. 4 has been converted from the positions of the detection regions 2 (pixels) into the energy values (eV) of the X-rays.
  • the horizontal axis of the spectrum are converted from an axis representing the positions of the detection regions 2 into an energy axis. In so doing, the energy axis of the spectrum is calibrated.
  • FIG. 7 is a flowchart illustrating an example of calibration processing executed by the processing unit 60 of the analysis device 100.
  • the spectrum generation unit 62 acquires data sets of peak positions and energy values (S 100).
  • the data sets are acquired by measuring a standard specimen using the analysis device 100.
  • the analysis device 100 measures the standard specimen, whereupon the spectrum generation unit 62 acquires the spectrum of the standard specimen, illustrated in FIG. 4 , and acquires information indicating the peak positions.
  • information indicating the energy values corresponding to the peak positions is acquired from a database of the energy values of the peaks (X-ray types) that are acquired by measuring the standard specimen. This database may be stored in the storage unit 54 in advance. Alternatively, the user may input information indicating the energy values in the peak positions through the operating unit 52.
  • the spectrum generation unit 62 uses the acquired data sets to determine the optimal solutions of the parameters, namely the incident angle oc, the distance D, and the height H of expression (2), by the method of least squares or the like (S 102).
  • the determined incident angle oc, distance D, and height H are stored in the storage unit 54.
  • the spectrum generation unit 62 determines the energy of the X-ray detected in each of the plurality of detection regions 2 by applying the determined incident angle oc, distance D, and height H to expression (2) (S104). More specifically, the spectrum generation unit 62 determines the energy detected in each of the plurality of detection regions 2 by determining the height H using expression (1) and determining the wavelength ⁇ from expression (2) using the determined height H.
  • the energy axis of the spectrum can be calibrated.
  • FIG. 8 is a flowchart illustrating an example of the spectrum generation processing executed by the processing unit 60 of the analysis device 100.
  • the specimen S is measured and a spectrum is acquired.
  • the analysis device 100 when the specimen S is irradiated with an electron beam by the electron beam emitting unit 10, X-rays are generated from the specimen S.
  • the X-rays generated from the specimen S are focused by the X-ray focusing mirror 20 and then enter the diffraction grating 30.
  • the X-rays that enter the diffraction grating 30 exit at exit angles corresponding to the wavelengths (the energy values) thereof and then enter the detection plane 43 of the image sensor 42.
  • the X-rays that enter the detection plane 43 are detected by the plurality of detection regions 2 arranged in the energy dispersion direction A.
  • the output signal output by the image sensor 42 is transmitted to the processing unit 60.
  • the spectrum generation unit 62 acquires information indicating the intensity of the X-ray detected in each of the plurality of detection regions 2 based on the output signal from the image sensor 42 (S200).
  • the spectrum generation unit 62 generates a spectrum based on the acquired information indicating the intensity of the X-ray detected in each of the plurality of detection regions 2 (S202). At this time, the spectrum generation unit 62 sets the energy axis of the spectrum based on the energy of the X-ray detected in each of the plurality of detection regions 2, which was determined in step S104.
  • the display control unit 64 executes control to display the spectrum generated by the spectrum generation unit 62 on the display unit 50 (S204).
  • the spectrum in FIG. 6 on which the horizontal and vertical axes respectively represent the energy values and intensities of the X-rays, is displayed on the display unit 50.
  • the calibration method according to this embodiment has the following effects, for example.
  • the calibration method includes a step of determining the energy of the X-ray detected in each of the plurality of detection regions 2 based on the positional relationship between the specimen S and the diffraction grating 30 and the positional relationship between the diffraction grating 30 and each of the plurality of detection regions 2. More specifically, in the calibration method according to this invention, the energy of the X-ray detected in each of the plurality of detection regions 2 is determined using expression (2).
  • the energy of the X-ray detected in each of the plurality of detection regions 2 is determined from the logical expression of the diffraction grating based on the positional relationship between the specimen S and the diffraction grating 30 and the positional relationship between the diffraction grating 30 and each of the plurality of detection regions 2.
  • the energy of the X-ray detected in each of the plurality of detection regions 2 is determined precisely over the entire range of energy values that can be detected by the image sensor 42. As a result, the energy axis of the spectrum is calibrated precisely.
  • the precision deteriorates dramatically outside the energy range between the peaks used in the correction.
  • the energy axis of the spectrum is corrected using a polynomial approximation, if the number of peaks used in the correction is small, the set constant necessarily decreases, and as a result, the precision likewise deteriorates.
  • the energy axis of the spectrum is corrected from the logical expression of the diffraction grating, and therefore the problems that occur with a polynomial approximation, as described above, do not arise.
  • the energy values of the detected X-rays is determined precisely in all of the detection regions 2 arranged in the energy dispersion direction A, for example.
  • the calibration method according to this invention also includes a step of measuring a standard specimen using the analysis device 100 and acquiring the spectrum of the standard specimen, and a step of determining the positional relationship between the specimen S and the diffraction grating 30 and the positional relationship between the diffraction grating 30 and each of the plurality of detection regions 2 based on the acquired spectrum of the standard specimen.
  • the energy of the X-ray detected in each of the plurality of detection regions 2 is determined using expression (2).
  • the incident angle ⁇ , the distance D, and the height H are determined from the spectrum of the standard specimen in step S12 in FIG. 3 .
  • the position (the height) of the specimen S, the position of the diffraction grating 30, and the position of the image sensor 42 can be adjusted based on the determined incident angle oc, distance D, and height H (height h).
  • the spectrum generation unit 62 executes processing for determining the energy of the X-ray detected in each of the plurality of detection regions 2 based on the positional relationship between the specimen S and the diffraction grating 30 and the positional relationship between the diffraction grating 30 and each of the plurality of detection regions 2.
  • the energy axis is calibrated more precisely than when calibration is performed using a polynomial approximation, for example.
  • the set energy axis can be corrected and set as a new energy axis.
  • the energy axis can be recalibrated.
  • a calibration method according to the first modification example will now be described.
  • a calibration method in which the energy axis of the spectrum of the specimen S, which is acquired by measuring the specimen S, is recalibrated will be described below.
  • the calibration method according to the first modification example further includes a step of measuring the specimen S and acquiring the spectrum of the specimen S using the analysis device 100, a step of setting the energy axis of the spectrum of the specimen S using the energy of the X-ray detected in each of the plurality of detection regions 2, which was determined in the step of determining the energy of the X-ray detected in each of the plurality of detection regions 2, a step of determining the positional relationship between the specimen S and the diffraction grating 30 based on the spectrum of the specimen S, a step of redetermining the energy of the X-ray detected in each of the plurality of detection regions 2 based on determined positional relationship between the specimen S and the diffraction grating 30, and a step of correcting the energy axis of the spectrum of the specimen S based on the redetermined energy of the X-ray detected in each of the plurality of detection regions 2.
  • FIG. 9 is a flowchart illustrating an example of the processing executed by the processing unit 60 of the analysis device according to the first modification example.
  • the specimen S is measured and a spectrum is acquired.
  • a spectrum on which the horizontal axis represents the positions of the detection regions 2 in the energy dispersion direction A and the vertical axis represents the intensities of the X-rays detected in the detection regions 2 is acquired.
  • the energy axis of the spectrum of the specimen S is set. More specifically, the horizontal axis of the spectrum is converted from an axis representing the positions of the detection regions 2 to an energy axis. At this time, the energy axis of the spectrum is set based on the energy of the X-ray detected in each of the plurality of detection regions 2, which was determined in step S14 (see FIG. 3 ).
  • FIG. 10 schematically illustrates an example of the spectrum of the specimen S.
  • a spectrum on which the horizontal axis represents an energy axis is acquired.
  • the positional relationship between the specimen S and the diffraction grating 30, or in other words the incident angle oc, is determined based on the spectrum of the specimen S.
  • the main cause of an error in the energy axis is deviation in the height Hs (see FIG. 5 ) of the specimen S. Therefore, by resetting the incident angle oc, which is the parameter relating to the height Hs of the specimen S, in expression (2), the energy axis can be corrected. Note that the distance D and the height H are fixed, and the values thereof determined in step S14 are used.
  • FIG. 11 illustrates a method for determining the incident angle ⁇ from the spectrum of the specimen S.
  • the optimal solution of the incident angle ⁇ is determined by the method of least squares or the like using expression (2) and using the peaks that have known energy values on the spectrum of the specimen S.
  • peaks appear in positions of E4eV, E5eV, and E6eV.
  • the X-ray type is specified, and the energy value of this X-ray type is E4DeV.
  • the logically or empirically determined energy value of the peak in the position of E4eV is E4DeV.
  • the logically or empirically determined energy value of the peak in the position of E6eV is E6DeV.
  • the incident angle ⁇ can be determined from expression (2) based on data sets of the energy values of the peaks on the spectrum and the logically or empirically determined energy values of the peaks.
  • the data sets are (E4, E4D) and (E6, E6D).
  • the energy of the X-ray detected in each of the plurality of detection regions 2 is determined from expression (2) using the incident angle ⁇ determined in step S24.
  • the energy axis of the spectrum in FIG. 10 is then corrected based on the redetermined energy of the X-ray detected in each of the plurality of detection regions 2.
  • FIG. 12 schematically illustrates the spectrum of the specimen S on which the energy axis has been corrected.
  • E4eV, E5eV, and E6eV have been corrected to E4DeV, E5DeV, and E6DeV, respectively.
  • the energy axis of the spectrum of the specimen S can be corrected.
  • the energy axis of the spectrum can be calibrated (recalibrated).
  • FIG. 13 is a flowchart illustrating an example of processing executed by the processing unit 60 to correct the energy axis.
  • the spectrum generation unit 62 acquires information indicating the intensity of the X-ray detected in each of the plurality of detection regions 2 based on the output signal from the image sensor 42, and generates the spectrum of the specimen S (S300). As a result, a spectrum on which the horizontal axis represents the positions of the detection regions 2 in the energy dispersion direction A and the vertical axis represents the intensities of the X-rays detected in the detection regions 2 is acquired.
  • the spectrum generation unit 62 sets the energy axis of the spectrum of the specimen S (S302).
  • the horizontal axis of the spectrum is converted from an axis representing the positions of the detection regions 2 to an energy axis.
  • the energy axis of the spectrum is set based on the energy of the X-ray detected in each of the plurality of detection regions 2, which was determined in step S104 (see FIG. 7 ).
  • a spectrum on which the horizontal axis represents the energy axis, as illustrated in FIG. 10 is acquired.
  • the display control unit 64 then executes control to display the spectrum of the specimen S in FIG. 10 , generated by the spectrum generation unit 62, on the display unit 50 (S304).
  • the spectrum generation unit 62 determines the positional relationship between the specimen S and the diffraction grating 30, or in other words the incident angle oc, based on the spectrum of the specimen S (S306).
  • the spectrum generation unit 62 determines the optimal solution of the incident angle ⁇ by the method of least squares or the like using expression (2) and using the peaks that have known energy values on the spectrum of the specimen S.
  • Information input by the user may be used as information relating to the peaks that have known energy values on the spectrum.
  • the user may specify a peak on the spectrum through the operating unit 52 and input the logically or empirically determined energy value of the specified peak.
  • the spectrum generation unit 62 redetermines the energy of the X-ray detected in each of the plurality of detection regions 2 from expression (2) using the determined incident angle ⁇ (S308).
  • the spectrum generation unit 62 generates a spectrum based on the energy of the X-ray detected in each of the plurality of detection regions 2, determined in step S308 (S310).
  • the spectrum generation unit 62 resets the energy axis of the spectrum by correcting the energy axis based on the energy of the X-ray detected in each of the plurality of detection regions 2, determined in step S308. As a result, the spectrum in FIG. 12 is generated.
  • the display control unit 64 executes control to display the spectrum of the specimen S in FIG. 12 , which was generated by the spectrum generation unit 62, on the display unit 50 (S312). As a result, the spectrum in FIG. 12 is displayed on the display unit 50. Note that the display control unit 64 may modify only the energy axis of the spectrum in FIG. 10 , displayed previously on the display unit 50, and display the modified spectrum on the display unit 50 as the spectrum in FIG. 12 .
  • the calibration method according to the first modification example further includes a step of determining the positional relationship between the specimen S and the diffraction grating 30 based on the spectrum of the specimen S, a step of redetermining the energy of the X-ray detected in each of the plurality of detection regions 2 based on determined positional relationship between the specimen S and the diffraction grating 30, and a step of correcting the energy axis of the spectrum of the specimen S based on the redetermined energy of the X-ray detected in each of the plurality of detection regions 2.
  • the energy axis can be recalibrated using the known peaks on the acquired spectrum. With the calibration method according to the first modification example, therefore, an accurate spectrum can be acquired without remeasuring, for example.
  • the X-rays generated from the specimen S are diffracted by the diffraction grating 30, but the spectroscopic element that diffracts the X-rays generated from the specimen S is not limited thereto, and a spectroscopic element capable of continuous energy dispersion of the X-rays may be used instead.
  • a zone plate or the like, for example, may be cited as this type of spectroscopic element.
  • the energy of the X-ray detected in each of the plurality of detection regions 2 can be determined using a logical expression.
  • the specimen S is irradiated with an electron beam, but X-rays may be generated from the specimen S by irradiating the specimen S with a primary beam other than an electron beam.
  • An X-ray beam, an ultraviolet beam, or the like may be cited as other types of primary beams.
  • the energy axis is calibrated using the spectrum of a standard specimen.
  • a spectrum of an unknown specimen by retrieving a matching spectrum from a database, information indicating the logically or empirically determined energy values of the peaks of the spectrum can be acquired in a similar manner to that employed with the spectrum of a standard specimen.
  • the energy axis can be calibrated in a similar manner to the embodiments described above using a spectrum of an unknown specimen.
  • FIG. 14 illustrates the positional relationship between the diffraction grating 30 and the image sensor 42.
  • the diffraction plane 31 of the diffraction grating 30 and the detection plane 43 of the image sensor 42 are perpendicular. Accordingly, the height H of the detection region 2 can be determined using expression (1).
  • the detection plane 43 of the image sensor 42 may be inclined relative to the diffraction plane 31 of the diffraction grating 30.
  • the height H can be determined using expression (3), whereupon the energy values detected in the detection regions 2 can be determined from expression (2). Hence, even when the detection plane 43 of the image sensor 42 is inclined, calibration can be performed in a similar manner to the embodiments described above.

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Claims (3)

  1. Kalibrierverfahren, das von einer Analysevorrichtung ausgeführt wird, wobei die Analysevorrichtung umfasst:
    ein spektroskopisches Element (30), das eingerichtet ist, um ein von einer Probe (S) durch Bestrahlen der Probe (S) mit einem Primärstrahl erzeugtes Signal zu beugen;
    einen Detektor (40), der eingerichtet ist, um das von dem spektroskopischen Element (30) gebeugte Signal zu erfassen und ein Spektrum des Signals zu gewinnen, und
    eine Speichereinheit (54),
    wobei der Detektor (40) eine Mehrzahl von Erfassungsbereichen (2) aufweist, die in einer Energiedispersionsrichtung (A) angeordnet sind,
    wobei das Kalibrierverfahren umfasst:
    Messen einer Standardprobe, indem die Analysevorrichtung (100) verwendet wird, um ein Spektrum der Standardprobe zu erfassen;
    Bestimmen einer Positionsbeziehung zwischen der Standardprobe und dem spektroskopischen Element (30) und einer Positionsbeziehung zwischen dem spektroskopischen Element (30) und jedem der Mehrzahl von Erfassungsbereichen (2) als optische Anordnungsparameter, basierend auf dem erfassten Spektrum der Standardprobe;
    Speichern der optischen Anordnungsparameter in der Speichereinheit (54);
    Bestimmen der in jedem der Mehrzahl von Erfassungsbereichen (2) erfassten Energie des Signals auf der Grundlage einer Positionsbeziehung zwischen der Probe (S) und dem spektroskopischen Element (30) und einer Positionsbeziehung zwischen dem spektroskopischen Element (30) und jedem der Mehrzahl von Erfassungsbereichen (2);
    Messen der Probe (S) unter Verwendung der Analysevorrichtung (100), um ein Spektrum der Probe (S) aufzunehmen;
    Einstellen einer Energieachse des Spektrums der Probe unter Verwendung von in jedem der Mehrzahl von Erfassungsbereichen (2) erfasster Energie des Signals, wobei eine in jedem der Mehrzahl von Erfassungsbereichen (2) erfasste Energie des Signals in dem Schritt des Bestimmens der in jedem der Mehrzahl von Erfassungsbereichen (2) erfassten Energie des Signals bestimmt worden ist;
    Bestimmen einer Positionsbeziehung zwischen der Probe (S) und dem spektroskopischen Element (30) basierend auf dem Spektrum der Probe (S) und der in der Speichereinheit gespeicherten optischen Anordnungsparameter, um einen durch eine Abweichung in der Höhe der Probe verursachten Fehler in der Energieachse zu korrigieren;
    Neubestimmen der in jedem der Mehrzahl von Erfassungsbereichen (2) erfassten Energie des Signals basierend auf der bestimmten Positionsbeziehung zwischen der Probe (S) und dem spektroskopischen Element (30); und
    Korrigieren der Energieachse des Spektrums der Probe (S) basierend auf der neu bestimmten Energie des in jedem der Mehrzahl von Erfassungsbereichen (2) erfassten Signals.
  2. Kalibrierverfahren nach Anspruch 1, bei dem das Signal ein Röntgenstrahl ist, und das spektroskopische Element (30) ein Beugungsgitter ist, das den Röntgenstrahl beugt.
  3. Kalibrierverfahren nach Anspruch 2, bei dem die Energie des in jedem der Mehrzahl von Erfassungsbereichen (2) erfassten Signals unter Verwendung des Ausdrucks d sin α − sin tan − 1 H / D = λ
    Figure imgb0008
     bestimmt wird,
    wobei d eine Gitterkonstante des Beugungsgitters ist, α ein Einfallswinkel ist, unter dem die Röntgenstrahlung in das Beugungsgitter eintritt, H eine Höhe jedes der Erfassungsbereiche relativ zu einer Beugungsebene des Beugungsgitters ist, D ein horizontaler Abstand von dem Beugungsgitter zu einer Erfassungsebene des Detektors ist, und λ eine Wellenlänge der Röntgenstrahlung ist.
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US5015069A (en) * 1989-02-17 1991-05-14 Linear Instruments Off axis rotation of diffraction grating
JP5576749B2 (ja) 2010-09-10 2014-08-20 日本電子株式会社 Ｘ線検出システム
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